Organic peroxides



United Sites Patent r ORGANIC PEROXIDES Nicholas A. Milas,'Belmont, Mass., assignor to Research Corporation, New York, N.Y., a corporation of New York a .rNo Drawing. Filed Ang..21, 1958, Ser. No. 756,295 4 Claims. I l.i260--610) This invention relates to a new group of organic peroxides and to a method of making them. 7

In my application Serial No. 417,860, filed March 27, 1954, now abandoned in favor of my application Serial No. 5,089, filed J anuary 25, 1960, I disclosed the production of useful organic peroxides by the application of ozone to unsaturated organic compounds in the presence of carbonium ions. I have now found that alkyl hydroperoxides-such as t-butylhydroperoxide, are not appreciably decomposed by ozone and in the presence of unsaturated organic compounds the hydroperoxides react with the intermediate ozone addition products to form a novel classof organic peroxides which are stable, cheap to manufacture, and useful as catalysts in polymerization reactions and as accelerators of diesel fuel combustion. They can also be converted to useful organic compounds.

The ozonization reactions involved in the present invention are in part also disclosed in my aforementioned application:

Ozonide In the foregoing formulas R represents hydrogen or a hydrocarbon radical, at least one R being a hydrocarbon radicalgand' R is a hydrocarbon radical.

If, the substituents R on one of thecarbon atoms of intermediates V and are the same as those on the other carbonatom, the intermediates are indistinguishable and the final products of reaction with the alkyl hydroperoxide arethe same; otherwise, the final products from the two possible intermediates are isomeric, as illustrated in specific Reaction 2 below.

The following specific examples will illustrate the principles of the invention: a

The present invention is not limited to tertiary alkyl hydroperoxides; secondary and primary alkyl hydroperoxides are also operable. Table I shows the peroxides produced from the olefins shown in column I.

TABLE I Organic peroxides from reaction of ozone with unsaturated compounds in the presence of t-butylhydroperoxide Yield of Unsaturated compound Peroxide peroxide per mole of 0;

used

Pentene-l 09111005 98.0 2-Methyl butene-Z H2005 87. 6 2,4,4-Tr1n1ethyl pentene-2. (311131504 95. 0 yclohexene. C10H2005 96. 0 lo-0cimene. CnHnOus 0 D-llmonene--- CiaHanOm 98. 6 wMethyl styrene 013112005 94. 6 trans-Stilbene 015112105 98. 0 2,5-Dirnethyl 2,5'-dlliydroxy-hexyne-3- 012111401 99. 5 9,IO-Dlmethylphenanthrene 010E340;

A more detailed description is given in the following illustrativeuexamples: p

EXAMPLE 1 A mixture of 2 g. of pentene-l and2.566 g. of t-butylhydroperoxide is made up with pure l-butyl alcohol to cc. and the solution allowed to absorb ozone at the rate of 0.0003718 mole per minute at 10 C. until an equivalent of one mole (0.02857 mole) of ozone per mole of pentene-l is absorbed. The mixture is then allowed to stand at room temperature for one hour and the peroxide formed determined quantitatively. A yield of 98.0% of peroxide based on the ozone used is obtained.

EXAMPLE 2 A mixture of 5 g. ofZ-methyl butene-Z and 6.43 g. of

t-butylhydroperoxide is made up to 100 cc. with pure tbutyl alcohol and the solution is allowed to absorb dry ozone at 10 C. at the rate of 0.0006275 mole of ozone per minute untilthe equivalent quantity (0.0710 'mole).

of'ozone per mole equivalent of Z-methyl butene-Z is absorbed. Themixture is then allowed to stand at room temperature for one hour-then the peroxide is determinedquantitatively. A'yield of 87.6% based on the of 95.0% of peroxide based on the ozoneused is found to be present.

EXAMPLE 4 A mixture of 5 g. of cyclohexene and 5.488 g. of 'tbutylhydroperoxide is made up to 100 cc. with t-butyl alcohol and the solution allowed to absorb dry ozone at at the rate of 0000696 mole ofozone per minute until the equivalent quantity (0.06098 mole) of ozone per mole equivalent of cyclohexene is absorbed. The mixture is then allowed to stand at room temperature for one hour and the peroxide present in the mixture is de terrnined quantitatively. A yield of 96.0% of peroxide based on the ozone used is found to be present.

EXAMPLE 5 A mixture of 2 g. of allo-ocimene and 3.97 g. of'tbutylhydroperoxide is made up to 100 cc. with pure tbutyl alcohol and-the solution allowed to absorb dry ozone at 10 C. at the rate of 0.0004724 mole per min. untila total of three mole-equivalents of ozone per mole of allo-ocimene is absorbed. The solution is then allowed to stand at room temperature for one hour and the peroxide present in the mixture isv determined quantitatively. A yield of 94.0% of peroxide is obtained.

EXAMPLE 6 A mixture of 5 g. of D-limonene and 6.62 g. of tbutylhydroperoxide is made up to 100 cc. with t-butyl alcohol and the solution allowed to absorb dry ozone at 10 at the rateof 0.0006736 mole per minute .until two mole-equivalents (0.07353 mole) of ozone per mole equivalent of D-limonene is absorbed. The solution is then allowed to stand at room temperature for one hour andthe peroxide is determined quantitatively; A yield of 98.6% of peroxide is obtained.

EXAMPLE (1' V A mixture of'S g. of a-methyl styrene and 3.8134 g. of .t-butylhydroperoxide is made up'to 100 be. with pure t-butyl alcohol and the solution allowed to absorb dry ozone at 10 C. atthe rate of 0.0005884 mole of ozone per minute until a totalof one mole-equivalent (0.042375 mole) of ozone per mole-equivalent of a-methyl styrene is absorbed. The solution is then allowed to stand at room temperature for one hour and the peroxide is determined quantitatively. A'yield of 94.6% of peroxide is obtained.

EXAMPLE 8 i A mixture of 2.5 g. ,of trans-stilbene and 1.25 g. of

termine'd' quantitatively. A'yield of 98.0%" of peroxide is obtained. 1

EXAMPLE 9 I A mixture of 2 g. of 2,5-dimethyl-2,S-dihydroxyhexyne- 3 and 1.2676 g; of etbutylhydroperoxidezis made up to 100 cc. with pure t-butyl alcohol and the solution allowed. to absorbsdry ozone at 10 C. 'at-the'rate 0600004249 mole per minute until. a total of one mole-equivalent (0.01408 mole) of. ozone per mole-equivalent "of 2,5-di- -methyl-2,5-dihydroxyhexyne-3j'is absorbed; The mixture is then allowed to stand at .room temperature for one hour and the peroxide present in determined quantitatively. A yield of 99.5% of peroxide is obtained.

EXAMPLE 1O 1 A solution of 0.5 g. of phenanthrene in 35 cc. of 90% t-butylhydroperoxide and 35 ccof di-t-butyl peroxide was allowed to absorb at -1 mole-equivalent-of ozone based on the amount of'phenanthrene'used. The product is allowed to warm to room-temperature and the solvent removed under reduced pressure (0.l mm.-). The residue is recrystallized several times from an" etherpentane mixture, M.P.' l54.8155'CI Analysis.Calcd. for C1BH2OO5 (I): c, 68.34; H, 637;"

for C H O -(II): C, 68.02; H, 7.27. Found: 0.69.60; H, 7.40.

The infrared spectrum of this peroxide shows-a weak band due to OH, no band due to C=O; strong bands due to -t-butyl groups and strong bands due to dialkyl peroxide, OO, groups. The peroxide has structure II with impurities of the peroxide 1.

EXAMPLE 11 A solution of 0.796 g. of 9,10-dimethylphenanthrene in a mixture of 20 cc. of %t-butyl hydroperoxide and 20 cc. of di-tbutyl peroxide is allowed to absorb at 0 of 1 mole-equivalent of ozone based on the amount of 9, IO-dimethylphenanthrene used. The solvent is then removed under reduced pressure (0.3 mm.) and the residue recrystallized from an ether-pentane mixture, M.P. 123124 C.

Analysis.-Calcd. for C H O (I): C, 69.75; H, 7.02; (O), 9.29; for Cal-1 0411): C, 69.20; H, 7.75; (O), 11.53. Found: (1,690,692; H, 7.0, 7.0; (O), 90:04

The infrared spectrum of this peroxide shows a weak band due to OH groups, no band due to C=O,

strong bands due to t-butyl groups and to dialkyl perabove peroxide has structurexlrather 'than"II.

on, on our 000mm): 1 I o -o r \O (I:\ 'C/ on, 000mm): bfioootonm EXAMPLE 12 A solution of 2.5 g. of trans-stilbene in a mixture of q 3.16 g. of t-butylhydroperoxide and 50 cc. of di-t-butyl peroxide is allowed to absorb at 10 1 mole-equivalent of ozone based on the trans-stilbene used. The mixture is then allowed to stand at 10 overnight, then the solvent removed at under reduced pressure (0.1 mm.). A highly viscous residue is obtained which failed to crystallize from several suitable solvents. This peroxide is stable at room temperature and when analyzed for active oxygen it gave values close to theoretical value.

Analysis.-Calcd. for C H O :(O), 10.06. Found: (0), 9.37 (average of several analyses).

From the decomposition products of this peroxide and analytical data, the following structure is found:

0 O O (CH 3 (3H a H H It is to be noted that while Examples 1-9 were carried out in t-butyl alcohol containing t-butylhydroperoxide, the experiments reported in the above examples were carried out in di-t-butyl peroxide containing t-butyl hydroperoXide and in the complete absence of t-butyl alcohol. This permits carrying out the ozonization below 0 C. thereby producing peroxides which are easier to isolate in the pure state. Industrially, however, t-butyl alcohol has an advantage since the peroxides produced are stable in solution and can be used directly in this solvent without isolation.

Although the examples given above are with tbutylhydroperoxide the invention is not limited to this hydroperoxide or to t-alkyl hydroperoxides.

I claim: 1. Organic peroxides of the formula OOR1 R OH I R l R/(I)(I)\R wherein R is selected from the group consisting of hydrogen and hydrocarbon radicals, at least one R being a hydrocarbon radical and R is an alkyl hydrocarbon radical.

2. Organic peroxides of the formula wherein R is selected from the group consisting of hydrogen and hydrocarbon radicals, at least one R being a hydrocarbon radical and R is a tertiary alkyl hydrocarbon radical.

3. A method of making organic peroxides of the formula wherein R is selected from the group consisting of hydrogen and hydrocarbon radicals, at least one R being a hydrocarbon radical and R is an alkyl hydrocarbon radical which comprises contacting a hydrocarbon of the formula with ozone in the presence of an alkyl hydroperoxide. 4. A method of making organic peroxides of the formula wherein R is selected from the group consisting of hydrogen and hydrocarbon radicals, at least one R being a hydrocarbon radical and R is a tertiary alkyl hydrocarbon radical which comprises contacting a hydrocarbon of the formula R v R Dickey Dec. 7, 1948 Pezzaglia Jan. 9, 1951 

1. ORGANIC PEROXIDES OF THE FORMULA 